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Title: Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation

Abstract

Metal organic frameworks (MOFs) have emerged as a novel platform offering new promise for photocatalytic applications. In this work, we report a mixed-node MOF (MOF-74) based on earth-abundant metals (i.e., Co and Fe) as highly active and robust photocatalysts for visible light-driven H2 generation. Using in situ X-ray absorption spectroscopy which allows us to selectively probe the individual metal node in MOFs, we unambiguously identified the catalytic active sites and captured the key intermediate species under the standard catalytic conditions. We show that both Co and Fe centers in MOF-74 are the reversible active sites, and the accumulation of their reduced states is responsible for the observed induction period for H2 generation. Moreover, we captured the key intermediate species formed when the reaction reaches equilibrium, which is featured by an elongated Co–O bond at the Co center and a more distorted octahedral geometry at the Fe center with respect to their original geometry. These results not only demonstrate the potential of MOF-74 as a single site catalyst for H2 generation but also provide new insight into the catalytic mechanism for further development.

Authors:
 [1];  [2];  [2];  [3];  [2];  [2]; ORCiD logo [4];  [3]; ORCiD logo [2]
+ Show Author Affiliations
  1. Wuyi Univ., Jiangmen (China); Marquette Univ., Milwaukee, WI (United States)
  2. Marquette Univ., Milwaukee, WI (United States)
  3. Wuyi Univ., Jiangmen (China)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Petroleum Research Fund (PRF); Wuyi University
OSTI Identifier:
1595943
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 2; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhou, Yixuan, Hu, Wenhui, Yang, Sizhuo, Zhang, Yunbo, Nyakuchena, James, Duisenova, Korlan, Lee, Sungsik, Fan, Donghua, and Huang, Jier. Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.9b09634.
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Zhou, Yixuan, Hu, Wenhui, Yang, Sizhuo, Zhang, Yunbo, Nyakuchena, James, Duisenova, Korlan, Lee, Sungsik, Fan, Donghua, & Huang, Jier. Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation. United States. https://doi.org/10.1021/acs.jpcc.9b09634
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Zhou, Yixuan, Hu, Wenhui, Yang, Sizhuo, Zhang, Yunbo, Nyakuchena, James, Duisenova, Korlan, Lee, Sungsik, Fan, Donghua, and Huang, Jier. Fri . "Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation". United States. https://doi.org/10.1021/acs.jpcc.9b09634. https://www.osti.gov/servlets/purl/1595943.
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@article{osti_1595943,
title = {Site-Selective Probes of Mixed-Node Metal Organic Frameworks for Photocatalytic Hydrogen Generation},
author = {Zhou, Yixuan and Hu, Wenhui and Yang, Sizhuo and Zhang, Yunbo and Nyakuchena, James and Duisenova, Korlan and Lee, Sungsik and Fan, Donghua and Huang, Jier},
abstractNote = {Metal organic frameworks (MOFs) have emerged as a novel platform offering new promise for photocatalytic applications. In this work, we report a mixed-node MOF (MOF-74) based on earth-abundant metals (i.e., Co and Fe) as highly active and robust photocatalysts for visible light-driven H2 generation. Using in situ X-ray absorption spectroscopy which allows us to selectively probe the individual metal node in MOFs, we unambiguously identified the catalytic active sites and captured the key intermediate species under the standard catalytic conditions. We show that both Co and Fe centers in MOF-74 are the reversible active sites, and the accumulation of their reduced states is responsible for the observed induction period for H2 generation. Moreover, we captured the key intermediate species formed when the reaction reaches equilibrium, which is featured by an elongated Co–O bond at the Co center and a more distorted octahedral geometry at the Fe center with respect to their original geometry. These results not only demonstrate the potential of MOF-74 as a single site catalyst for H2 generation but also provide new insight into the catalytic mechanism for further development.},
doi = {10.1021/acs.jpcc.9b09634},
journal = {Journal of Physical Chemistry. C},
number = 2,
volume = 124,
place = {United States},
year = {2019},
month = {12}
}
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https://doi.org/10.1021/acs.jpcc.9b09634
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